Binary catalyst systems for the polymerization of unsaturated alicyclic monomers

ABSTRACT

There is disclosed a process for the ring opening polymerization of certain unsaturated alicyclic compounds such as cyclobutene, cyclopentene, cyclooctene, cyclooctadiene and the like which comprises subjecting such compounds to a two component catalyst system, the first component being an alkali metal compound of tungsten hexahalide or an alkyl amine derivative of tungsten hexahalide; the second component being an aluminum alkyl, an aluminum halide, an aluminum alkyl hydride or a tin alkyl halide.

nited States Patent [72] Inventor William Allen .ludy

Akron, Ohio 21 1 Appl. No. 795,693 [22] Filed Jan.31, 1969 [45] PatentedNov. 30, 1971 [73] Assignee The Goodyear Tire & Rubber Company Akron,Ohio (54] BINARY CATALYST SYSTEMS FOR THE POLYMERIZATION 0F UNSATURATEDALlCYCLlC MONOMERS 12 Claims, No Drawings [52] U.S. Cl 260/88.2,260/8078. 260/821, 260/93.1, 260/943 [51] C081 19/04 [50] 260/931, 88.2,80.78

[56] Relerences Cited UNITED STATES PATENTS 3,074,) 18 1/1963 Eleuterio260/93.l 3,449,310 6/1969 Dall'Asta et a1. 260/93.1

Primary Examiner-.loseph L. Schoter Axsislanl Examiner-Richard A.Gaither Anomey.r F. W. Brunner and .1. Y. Clowney ABSTRACT: There isdisclosed a process for the ring opening polymerization of certainunsaturated alicyclic compounds such as cyclobutene. cyclopentene.cyclooctene. cyclooctadiene and the like which comprises subjecting suchcompounds to a two component catalyst system, the first component beingan alkali metal compound of tungsten hexahalide or an alkyl aminederivative of tungsten hexahalide; the second component being analuminum alkyl, an aluminum halide. an aluminum alkyl hydride or a tinalkyl halide.

BINARY CATALYST SYSTEMS FOR THE POLYMERIZATION QF UNSATURATED ALICYCLICMONOMERS i v This invention relates to a process for polymerizingunsaturated alicyclic compounds and to the products resulting therefrom.In its broad aspect, the invention is directed to the preparation ofpolymers derived from unsaturated alicyclic compounds which contain atleast one alicyclic ring structure containing at least two carbon atomsconnected through a double bond.

The polymerization process of this invention may be used to preparenovel solid polymers. The properties and characteristics of thesepolymers can be ftailor made" to ma wide variety of uses and fields ofapplication. The properties of the polymers resulting from thepolymerization process of this invention'can be varied over a wide rangedepending on l the particular unsaturated alicyclic monomer chosen to bepolymerized, (2) the particular polymerization catalyst employed and (3)the particular polymerization conditions employed. The productsresulting from the polymerization of this invention can be employed in avariety of applications; for example, when they are elastomeric innature, they may be employed to produce finished rubber articles such aspneumatic tires, molded goods and the like or when they are plastic innature, they may be materials which are useful to manufacture articlessuch as films and fibers and also useful to form finished products bymolding techniques.

This invention comprises the ring opening polymerization of at least oneunsaturated alicyclic compound selected from the group consisting of (l)unsaturated alicyclic compounds containing at least four and not morethan five carbon atoms in the cyclic ring and containing one carbon tocarbon double bond in the cyclic ring and (2) unsaturated alicycliccompounds containing at least 8 carbon atoms in the cyclic ring andcontaining at least one carbon to carbon double bond in the cyclic ringby subjecting said alicyclic compounds to ring opening polymerizationconditions in the presence of a catalyst system comprising (A) at leastone material selected from a class consisting of compounds of thegeneral formulas:

l MWX and 2 I) a) a) 4) N 1 s Wherein M is a metal selected from thegroup consisting of potassium, rubidium, cesium and thallium; R R 1 andR represent at least one alkyl group containing from one to two carbonatoms; W represents tungsten; N represents nitrogen and X represents amember of a group consisting of chloride and bromide ions and (B) atleast one metal compound selected from a group consisting of compoundsof the general formulas:

( l R,,AlX;, wherein n is an integer from O to 3,

(2) R,,All-l;, wherein n is an integer from I to 2 and (3) R,,SnX,wherein n is an integer from O to 4 and also wherein R represents alkyl,aryl, alkaryl and aralkyl groupsiAl represents aluminum, Sn representstin; H represents hydrogen and X represents halogen.

Representative examples of the compound selected from a group ofcompounds having the formula MWX useful as the first or (A) catalystcomponent of this invention includes potassium hexachlorotungstate,potassium hexabromotungstate, rubidium hexachlorotungstate, rubidiumhexabromotungstate, cesium hexachlorotungstate, cesiumhexabromotungstate, thallium hexachlorotungstate and thalliumhexabromotungstate. i

Representative examples of the compound selected from a group ofcompounds having the formula:

useful as the first or (A) catalyst component of this invention includetetramethylammonium tetramethylammonium hexabromotungstate,tetraethylammonium hexachlorotungstate, tetraethylammoniumhexabromotungstate, dimethyldiethylammonium hexachlorotungstate,dimethyldiethylammonium hexabromotungstate and the like. The mostpreferred material useful as the first or (A) catalyst component of thisinvention is potassium hexachlorotungstate.

The metal compound useful as the second or (8) catalyst component may bedefined by the general formula:

I I n -1n i where n is an integer from O to 3 and includes aluminumhalides; alkyl, aryl, alkaryi and aralkyl aluminum halides and dihalidesand trialkyl, triaryl, trialkaryl and triaralkyl aluminum compounds.Representative examples of such compounds include aluminum chloride,aluminum bromide, ethylaluminum dichloride, ethylaluminum dibromide,npropylaluminum dichloride, isobutylaluminum diiodide, phenylaluminumdibromide, tolylaluminum dibromide, phenylaluminum diiodide,tolylaluminum diiodide, benzylaluminum dibromide, diethylaluminumchloride, di-n-propylaluminum chloride, diisobutylaluminum chloride,diethylaluminum bromide, diethylaluminum iodide, diethylaluminumfluoride, diphenylaluminum chloride, ditolylaluminum chloride,dibenzylaluminum bromide, trimethylaluminum, triethylaluminum,tri-n-propylaluminum, trihexylaluminum, triphenylaluminum,tritolylaluminum, tribenzylaluminum and the like.

The metal compound useful as the second or (B) catalyst component may bedefined by the general formula:

where n is an integer from 1 to 2 and includes alkyl, aryl, alkaryl andaralkyl aluminum hydrides and dihydrides. Representative examples ofsuch compounds include diphenylaluminum hydride, diethylaluminumhydride, dimethylaluminum hydride, diisobutylaluminum hydride,phenylaluminum dihydride, ethylaluminum dihydride, di-n-propylaluminumhydride and the like.

The metal compound useful as the second or (B) catalyst component isdefined by the formula:

where n is an integer from 0 to 4 and includes tetraalkyl, tetraaryl,tetraalkaryl and tetraaralkyl tin compounds; alkyl, aryl, alkaryl andaralkyl tin halides, dihalides and trihalides and tin halide compounds.Representative examples of such compounds include tetraethyltin,tetramethyltin, tetraphenyltin, tetratolyltin, triethyltin chloride,triisoamyltin chloride, triphenyltin chloride, tribenzyltin chloride,diethyltin dichloride, diethyltin difluoride, methyltin trichloride, tintetrachloride, tin tetrabromide and the like.

The catalysts employed in this invention are prepared by mixing thecomponents by known techniques. Thus, the catalysts may be prepared bypreformed or in situ" techniques. By preformed is meant the manner inwhich the catalyst components are mixed together prior to exposure ofany of the catalyst components to the monomer to be polymerized. By insitu" is meant that the catalyst components are added separately to themonomer to be polymerized. The catalyst components can be mixed eitheras pure compounds or as suspensions or solutions in liquids which do notadversely afiect the ring opening polymerization. While the presence ofthe monomeris notessential during the formation of an active catalystspecies by a mixing of (A) and (B) and this fact facilitates the use ofpreformed catalysts, it has been found that freshly preformed catalystsare generally more active than catalysts which have been allowed to agebefore use.

The amount of catalyst employed may be varied over a wide range ofconcentrations. Any establishment of an arbitrary catalyticconcentration for one of the catalyst components will determine therelative concentrations of the remaining catalyst component. Thus, therelative concentrations of the catalyst components, (A) and (B), areinterdependent. This hexachlorotungstate, interdependency of thecatalyst components (A) and (B also depends on a number of other factorssuch as temperature, reactant used, purity of reactant, reaction timesdesired and the like. Of course, a catalytic amount, about 5X 1 0'moles, of catalyst must be employed and those skilled in the art will bereadily able to determine the optimum catalytic range.

It has been found that successful results are obtained in the practiceof this invention when the molar relationship between the catalystcomponents (A) and (B), as previously defined, are within a molar ratioof A/B ranging from 0.0 l l .0 to about 5.0/1.0.

Various unsaturated alicyclic compounds may be employed in the practiceof this invention. As is mentioned above, unsaturated alicycliccompounds containing at least four and not more than five carbons atomsin the cyclic ring which contain one carbon-to-carbon double bond in thecyclic ring and unsaturated alicyclic compounds containing at leasteight carbon atoms in the cyclic ring which contain at least onecarbon-tocarbon double bond in the cyclic ring are operable in thisinvention.

The preferred unsaturated alicyclic compounds of this invention arethose comprising a single unsaturated alicyclic ring. These alicyclicrings may be monoor multisubstituted by such groups as alkyl,aryljarylalkyl and halogen groups.

Representative examples of unsaturated alicyclic compounds containing asingle alicyclic ring having at least four and not more than five carbonatoms in the cyclic ring and containing one double bond in said ring arecyclobutene and cyclopentene. Representative examples of compoundshaving' at least eight carbon atoms in the cyclic ring and having fromone to two double bonds in said ring are cyclooctene; 1,4- and1,5-cyclooctadiene. Representative of compounds having nine carbon atomsand one to three double bonds in the ring are cyclononene, 1,4- andl,5--cyclononadiene and 1,4,7- cyclononatriene. Representative ofcompounds having carbon atoms and one to three double bonds in the ringare cyclodecene, l,4-, 1,5- and 1,6-cyclodecadiene and 1,4,6- and1,4,7-carbon atoms and one to three double bonds in the ring arecycloundecene, 1,4-, and 1,6-cycloundecadienes and 1.4.7- andl,4,8-cycloundecatriene. Representative of compounds having l2 carbonatoms and one to three double bonds in the ring are cyclododecene, 1,4-,1,5-, 1,6-, and 1,7- cyclododecadiene and 1,4,7-, 1,4,8-, 1,4,9- and1,5,9- cyclododecatriene.

The most preferred unsaturated alicyclic compounds of this invention arethose containing from one to three carbon-tocarbon double bonds in thering and in which the double bonds are located in relation to each otherin a manner that they are not adjacent and are nonconjugated.Representative examples of such preferred materials are cyclobutene,cyclopentene, cyclooctene, cyclododecene and l,5-cycloctadiene and1,5,9-cyclododecatriene.

Still another class of preferred unsaturated alicyclic monomers arethose containing one carbon-to-carbon double bond in the ring of atleast four and not more than five carbon atoms, examples of which arecyclobutene and cyclopentene. Another group which are preferred arethose which have at least eight carbon atoms in the ring and not morethan 12 carbon atoms in the ring and contain one, two or threecarbon-tocarbon double bonds in said ring, examples of which arepreviously set forth.

Representative examples of substituted unsaturated alicyclic compoundsare alkyl-substituted compounds such as1,5,9-trimethylcyclododecatriene; aryl-substituted compounds such as3-phenylcyclooctene-l; aralkyl-substituted compounds such as 3-benzylcyclooctene-l; alkaryl-substituted compounds such as-3-methylphenylcyclooctene-l; halogen-substituted compounds wherein thehalogens are iodine, chlorine, bromine and fluorine such as5-chlorocyclooctenel; 3-bromocyclooctenel 5-chlorocyclododecene-l and5,6-dichlorocyclooctene-l. Mixtures of the unsaturated alicycliccompounds may be polymerized including-both substituted unsaturatedalicyclic compounds and the unsubstituted unsaturated alicycliccompounds.

The polymerizations of this invention may be conducted in solution or inbulk. When the polymerization is carried out in solution, solvents whichdo not adversely affect the polymerization are desired. Representativeof useful solvents are liquid aromatic hydrocarbons such as benzene andtoluene; hydrogenerated aromatic hydrocarbons such as tetralin; liquidaliphatic hydrocarbons such as pentane, heptane, hexane, petroleumether, decane; and alicyclic hydrocarbons such as cyclohexane, decalinand cyclooctane. Mixtures of such solvents may also be used.

Temperatures at which the polymerization reaction is carried out can bevaried over a wide range. Usually the temperature can be varied fromextremely low temperatures such as 60 C. up to high temperatures such as150 C. or higher. Thus, the temperature is not a critical factor of theinvention. It is generally preferred, however, to conduct the reactionat a temperature in the range of from about 20 C. to about C. Thepressure at which the polymerization is carried out can also be variedover a wide range. The reaction can be conducted at atmospheric pressureor, if desired, it can be carried out at subatmospheric pressure orsuperatmospheric pressure. Generally a satisfactory polymerization isobtained when the reaction is carried out at about autogenous pressure,developed by the reactants under the operating conditions used.

The polymerization time will vary and can range from a few seconds to 24hours or more, depending upon the polymerization conditions and thedegree and extent of polymerization desired.

The polymerization reaction may be carried out as a batch or as acontinuous process. In preforming the polymerizations of this invention,the introduction of the monomer, catalyst and solvent, when a solvent isemployed, can each be made to the reaction zone alternately,intermittently, and/or continuously.

It is thought that the polymerizations of this invention take placethrough a ring-opening polymerization mechanism. Such ring-openingpolymerizations of unsaturated alicyclic compounds can be used to make anumber of alternating copolymers and terpolymers that have not beencapable of being made before. For example, the ring-openingpolymerization of cyclooctene yields a polyoctenamer which may beconsidered the alternating copolymer of one butadiene unit and twoethylene units.

The ring opening polymerization of cyclooctadiene-l,5 leads to apolybutenamer which is equivalent to the IA addition polymer ofbutadiene-l,3. In practicing this invention, polybutenamers can beformed whose structure comprises alternating cis and transvinylenegroups in successive polymeric repeat units which is equivalent to thepolymer which may be obtained by the 1,4-addition polymerization ofbutadiene-l,3 in which successive butadiene-l,3 units alternately occurin cisand transconfigurations. Such a polymer could be considered analternating copolymer of cis and trans 1,4 poly(butadiene-l ,3

The ring opening polymerization of S-methylcyclooctene-l would yield thealternating terpolymer of butadiene-l,3, propylene and ethylene;likewise, S-phenylcyclooctene-l would yield the alternating terpolymerof butadiene-l,3, styrene and ethylene. The ring opening polymerizationof5- methylcyclooctadiene-l,5 would yield the alternating copolymer ofbutadiene-l,3 and isoprene. The ring opening polymerization ofsubstituted cyclododecenes can yield even more complicated alternatingcopolymers, terpolymers and even quadripolymers.

Ring opening polymerization also allows one to make copolymers andterpolymers that have not heretofore been made by ordinary additionpolymerizations. A representative example of such a polymerization isthe ring-opening polymerization of cyclononene which yields theperfectly alternating copolymer of butadienel ,3 and pentamethylene.

Ring opening polymerization of halogen-substituted unsaturated alicyclicmonomers also leads to interesting copolymers and terpolymers; forinstance, 5-chlorocyclooctene-l would lead to a polymer equivalent to analternating interpolymer of butadiene-l,3 plus vinyl chloride andethylene; 3-bromocyclooctene-l would yield a polymer equivalent to analternating interpolymer of ethylene plus l-bromobutadiene-l,3 andethylene and 5-chlorocyclododecene-l would lead to a polymer equivalentto an alternating interpolymer of butadienel ,3 plus vinyl chloride and3 ethylene molecules.

Ring opening polymerization of unsaturated alicyclic hydrocarbonscontaining at least four and not more than five carbon atoms andcontaining one carbon-to-carbon double bond in the cyclic ring and thosecontaining eight carbon atoms and at least one carbonto-carbon doublebond in the cyclic ring produces high molecular weight polymers whichhave a high degree of resistance to oxidation.

Bulk polymerizations may be desirable from a process standpoint asrelatively little heat appears to be evolved per mole of unsaturatedalicyclic monomer polymerized in practicing this invention. Thisconstitutes a great advantage for this ring opening type ofpolymerization over conventional addition polymerization.

The low volume decrease accompanying a ring-opening polymerization isanother major advantage over conventional addition polymerization,particularly where these monomers are bulk polymerized to form pottingcompounds and various articles, examples of which are molded plasticmaterials, molded rubberlike goods, shoe soles and heels, industrialbelts and vehicle tires.

In these applications the monomer may be polymerized in the presence ofone or more reinforcing carbon blacks, pigments or resins and certainantioxidants. The products made by this procedure may be cross-linked byadding polymerizable polyfunctional compounds, for example,bicyclopentadiene, to the main monomer. The molded products made byring-opening polymerization may be cross-linked by exposure to ionizingradiation such as gamma rays, X-rays, or electrons. These moldedproducts may also be cross-linked or vulcanized by incorporating certaincompounds which on heating during or subsequent to the polymerizationwill lead to conventional cross-linking or vulcanization of thesepolymers.

The polymerization reaction may be terminated by incorporating variouscompounds which, upon heating, release materials which deactivate thecatalyst. Representative examples of such compounds are the ammoniasalts such as ammonium chloride, ammonium carbonate, ammonium acetate,ammonium oleate, ammonium sulfate and ammonium phosphate; otherammonia-releasing compounds such as tetraalkyl ammonium halides, e.g.,tetramethyl ammonium chloride, water-releasing agents such as salts withwater of crystallization, examples of which are: Al (SO )'l7 H O;NH,Al(SO,,) -12 H O; FeS0 -7 H O; MgHPO -7 H O; KAL(SO l2 H O; KNaCO -61-1 0; Na B O,-l0 H O; Na CO "'l0 H O; NaHPO -l2 H O; Na So 'l0 H 0; andZn- NO -6 H O.

The following examples are set forth to further illustrate the nature ofthis invention. However, it should be understood that the examples areset forth for illustrative and not for limitative purposes. Allexperiments were conducted in an atmosphere of nitrogen unless notedotherwise.

EXAMPLE 1 A series of polymerizations was carried out using 17.0 grams(g.) of freshly distilled cyclooctene and 80 milliliters (ml.) of drybenzene in each polymerization. All manipulations of charging monomer,solvent and catalyst components were conducted under a nitrogenatmosphere. The catalyst components were used as a 0.10 molar (M) slurryof potassium hexachlorotungstate (KWCI in benzene, a 0.20 M slurry offinely divided aluminum chloride (AlCl in cyclohexane, a 0.20 M slurryof finely divided aluminum bromide (AlBr in cyclohexane and a 0.20 Msolution of ethylaluminum dichloride (EADC) in benzene. Allpolymerizations were commenced by first injecting 2X10 moles of KWClinto each polymerization bottle followed by the immediate injection ofthe (B) catalyst components in amounts as listed in the of a 10 percentby weight solution of ditertiary butyl-p-cresol in a 50/50 mixture ofmethanol and benzene.

While certain representative embodiments and details have been shown forthe purpose of illustrating the invention, it will be apparent to thoseskilled in the art that various changes and modifications may be madetherein without departing from the spirit or scope of the invention.

We claim:

1. A process comprising a ring-opening polymerization of at least oneunsaturated alicyclic compound selected from the group consisting of (1)unsaturated alicyclic compound containing four to five carbon atoms inthe cyclic ring and containing one carbon to carbon to carbon doublebond in the cyclic ring and (2) unsaturated alicyclic compoundscontaining eight to twelve carbon atoms inclusive in the cyclic ring andcontaining at least one carbon to carbon double bond in the cyclic ring,by subjecting said alicyclic compounds to ring opening polymerizationconditions, in the presence of a catalyst system comprising (A) at leastone material selected from a class consisting of compounds of thegeneral formulas:

l. MWX and 2. WX wherein M is a metal selected from the group consistingof potassium, rubidium, cesium and thallium; R,, R R and R represent atleast one alkyl group containing from one to two carbon atoms; Wrepresents tungsten; N represents nitrogen and X represents a member ofa group consisting of chloride and bromide ions and (B) at least onemetal compound selected from a group consisting of compounds of thegeneral formulas:

l. R,,AlX wherein n is an integer from 0 to 3,

2. R,,All1 wherein n is an integer from 1 to 2 and 3. R,,SnX wherein nis an integer from 0 to 4 and also wherein R represents alkyl, aryl,alkaryl and aralkyl groups; Al represents aluminum, Sn represents tin, Hrepresents hydrogen and X represents halogen.

2. A process according to claim 1 in which the molar relationshipbetween the catalyst components defined by (A) and (B) are within themolar ratio of A/B ranging from about 0.01/10 to about 5.0/1 .0.

3. A process according to claim 1 in which the (A) catalyst component ispotassium hexachlorotungstate.

4. A process according to claim 1 in which the organometallic or (B)catalyst component is an alkyl aluminum halide.

5. A process according to claim 1 in which the (B) catalyst component isan aluminum halide compound.

6. A process according to claim 1 in which the unsaturated alicycliccompound contains four to five carbon atoms in the cyclic ring and onlyone carbon to carbon double bond in the cyclic ring.

7. A process according to claim 1 in which the unsaturated alicycliccompound contains eight to 12 carbon atoms inclusive in the cyclic ringand contains from one to three carbon to carbon double bonds in thecyclic ring which are located in a relation to each other that they arenot conjugated.

8. A process according to claim 1 in which cyclooctene ishomopolymerized.

9. A process according to claim 1 in which cyclooctadiene ishomopolymerized.

10. A process according to claim 1 cyclododecatriene is homopolymerized.

11. A process according to claim 1 in which cyclooctadiene andcyclododecatriene are copolymerized.

12. A process according to claim 1 in which the (A) catalyst componentis potassium hexachlorotungstate and the (B) in which table below.Termination was accomplished by injecting 5 ml. catalyst component is analuminum halide.

22;;3? UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,62%060 med November 30, 1971 Inv n fl William Allen Judy It iscertified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

' Claim 1, line 31, delete "wx and insert Signed and sealed this 23rdday of January 1973.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. ROBERT QOTTSCHALK Attesting OfficerCOIYHlllSSlOIlEI of Patents

2. A process according to claim 1 in which the molar relationshipbetween the catalyst components defined by (A) and (B) are within themolar ratio of A/B ranging from about 0.01/1.0 to about 5.0/1.0. 2.((R1) (R2) (R3) (R4) N ) WX6 wherein M is a metal selected from thegroup consisting of potassium, rubidium, cesium and thallium; R1, R2, R3and R4 represent at least one alkyl group containing from one to twocarbon atoms; W represents tungsten; N represents nitrogen and Xrepresents a member of a group consisting of chloride and bromide ionsand (B) at least one metal compound selected from a group consisting ofcompounds of the general formulas:
 2. RnAlH3 n wherein n is an integerfrom 1 to 2 and
 3. RnSnX4 n wherein n is an integer from 0 to 4 and alsowherein R represents alkyl, aryl, alkaryl and aralkyl groups; Alrepresents aluminum, Sn represents tin, H represents hydrogen and Xrepresents halogen.
 3. A process according to claim 1 in which the (A)catalyst component is potassium hexachlorotungstate.
 4. A processaccording to claim 1 in which the organometallic or (B) catalystcomponent is an alkyl aluminum halide.
 5. A process according to claim 1in which the (B) catalyst component is an aluminum halide compound.
 6. Aprocess according to claim 1 in which the unsaturated alicyclic compoundcontains four to five carbon atoms in the cyclic ring and only onecarbon to carbon double bond in the cyclic ring.
 7. A process accordingto claim 1 in which the unsaturated alicyclic compound contains eight to12 carbon atoms inclusive in the cyclic ring and contains from one tothree carbon to carbon double bonds in the cyclic ring which are locatedin a relation to each other that they are not conjugated.
 8. A processaccording to claim 1 in which cyclooctene is homopolymerized.
 9. Aprocess according to claim 1 in which cyclooctadiene is homopolymerized.10. A process according to claim 1 in which cyclododecatriene ishomopolymerized.
 11. A process according to claim 1 in whichcyclooctadiene and cyclododecatriene are copolymerized.
 12. A processaccording to claim 1 in which the (A) catalyst component is potassiumhexachlorotungstate and the (B) catalyst component is an aluminumhalide.